Composition and process for treating keratinic substances with at least one anionic polymer and at least one quaternized protein

ABSTRACT

Composition and process for treating keratinic substances with at least one anionic polymer and at least one quaternized protein. The invention concerns a process for the cosmetic treatment of keratinic substances and in particular hair, the skin or the nails, wherein at least one strongly cationic quaternized protein and at least one anionic polymer other than homopolymers of acrylic acid crosslinked by means of a polyfunctional agent or an amphoteric polymer are applied on the said substances.

This is a divisional of application Ser. No. 07/284,683, filed on Dec.15, 1988, which was a divisional of application Ser. No. 06/665,386,filed on Oct. 26, 1984 now U.S. Pat. Nos. 5,008,105 and 4,796,646respectively.

The present invention relates to new, polymer-based compositionsintended to be employed in the treatments of keratinic substances andmore particularly in the cosmetic treatment of hair, skin and nails.

Cosmetic treatment is understood to mean all the treatments which makeit possible to condition, wash and/or colour keratinic substances suchas hair, the skin or the nails.

The Applicant Company has already described in French Patent 2,383,660compositions based on anionic polymers and on cationic polymers for thetreatment of keratinic substances. These compositions make it possibleto impart to hair properties of firmness, shape-retention, body, sheen,easy disentangling and pleasant touch.

The quaternised proteins which may be employed according to theinvention are known in themselves and have already been recommended foruse in cosmetics.

The quaternised proteins more particularly preferred according to theinvention are strongly substantive proteins whose substantivity can becompared to cationic polymers containing quaternary ammonium groups suchas the water-soluble cyclopolymers mentioned in the Applicant Company'searlier French Patent No. 2,383,660 such as in particular the copolymerof dimethyl diallyl ammonium chloride and acrylamide of molecular weightabove 500,000, such as the polymers sold under the name MERQUAT 550 bythe MERCK Company.

When these polymers are combined with anionic polymers they impart tothe treated hair good disentangling properties and shape-retention andfirmness properties.

When they are not combined with the anionic polymer, the quaternisedproteins according to the invention impart body and disentanglement,sheen, and pleasant touch to the hair.

The Applicant Company has discovered that their use in combination withanionic polymers such as defined below permitted, in addition to theremarkable properties of disentanglement, body, sheen and touch, tostrengthen the shape-retention and firmness properties of hair, whichoffers an undoubted benefit to the users.

These properties are clearly superior when compared to the properties ofthe combination of a polymer having a similar substantivity with thesame anionic polymer.

A subject of the present invention is thus a process for treatingkeratinic substances making use of an anionic polymer and a cationicpolymer which is a strongly cationic quaternised protein.

Another subject consists of the compositions employed in such a process.

Other subjects will appear from the reading of the description and theexamples which follow.

The process for treatment of keratinic substances and preferablycosmetic treatment of hair, the skin and/or the nails, according to theinvention, is essentially characterised in that at least one stronglycationic quaternised protein and at least one anionic polymer with theexception of homopolymers of acrylic acid which are crosslinked by meansof a polyfunctional agent are applied to the said substance.

The quaternised proteins which are more particularly capable of beingemployed according to the invention correspond to the formula: ##STR1##in which A denotes a protein residue derived from hydrolysates ofcollagen protein, R denotes a lipophile group containing up to 30 carbonatoms and preferably containing 10-20 carbon atoms and namely 12 to 14carbon atoms, and X denotes an alkylene group containing 1 to 6 carbonatoms.

The preferred quaternised proteins have a molecular weight of between1,500 and 10,000 and preferably between 2,000 and 5,000.

A more particularly preferred product is the product sold under the nameLEXEIN QX-3000 recommended in the CTFA dictionary under the name"Cocotrimonium collagen hydrolysate" and marketed by the Inolex Company.

The anionic polymers which can be employed in the process according tothe invention are polymers having a molecular weight of between 500 andapproximately 5,000,000 and advantageously between 10,000 and 3,000,000and have a large number of sulphonic, carboxylic or phosphoric groups.These polymers can also be anionic latices.

The anionic polymers which can be employed in accordance with theinvention may be chosen in particular from the polymers derived from acarboxylic or sulphonic acid, mentioned in the Applicant Company'sFrench Patent 2,383,660.

The carboxylic groups are provided in the anionic polymers byunsaturated mono- or dicarboxylic acids denoted particularly by theformula: ##STR2## in which n is an integer from 0 to 10, A denotes amethylene group optionally joined to the carbon atom of the unsaturatedgroup or to the adjoining methylene group when n is greater than 1through the intermediacy of a heteroatom such as oxygen or sulphur, R₁denotes a hydrogen atom or a phenyl or benzyl group, R₂ denotes ahydrogen atom or a lower alkyl group or a carboxy group, R₃ denotes ahydrogen atom, a lower alkyl group, --CH₂ -- COOH, phenyl, or benzyl.

In the abovementioned formula a lower alkyl radical denotes preferably agroup containing 1 to 4 carbon atoms and in particular methyl, ethyl andthe like.

The preferred anionic polymers employed according to the invention arechosen from: - homo- or copolymers of acrylic or metacrylic acid ortheir salts and in particular the products sold under the names VERSICOLE or K by the Company ALLIED COLLOID, ULTRAHOLD 8 by the Company CIBAGEIGY, the copolymers of acrylic acid and acrylamide sold in the form oftheir sodium salt under the names RETEN 421, 423 or 425 by the HERCULESCompany, sodium polymethacrylate sold under the name DARVAN No. 7 by theVan der Bilt Company, the alkali metal salts of polyhydroxycarboxylicacids sold under the name HYDAGEN F by the HENKEL Company; - copolymersof the abovementioned acids with a monoethylenic monomer such asethylene, vinylbenzene, vinyl or allyl esters, esters of acrylic ormethacrylic acids, optionally grafted on a polyalkylene glycol such aspolyethylene glycol and optionally crosslinked. Such polymers aredescribed in particular in French Patent 1,222,944 and GermanApplication 2,330,956; copolymers of this type containing an optionallyN-alkylated and/or hydroxyalkylated acrylamide moiety in their chainsuch as are described in particular in Luxemburg Patents 75,370 and75,371; acrylic acid homopolymers crosslinked with the aid of apolyfunctional agent such as the group in their chain, andmonoesterified or monoamidified, described in French Patents 2,350,834and 2,357,241 of the Applicant Company.

The polyacrylamide containing carboxylate groups such as those sold bythe American Cyanamid Company under the name CYANAMER A 370.

The polymers with a sulphonic group which may be employed in accordancewith the invention are chosen in particular from

Salts of polystyrenesulphonic acid such as the sodium salts sold underthe name Flexan 500 having a molecular weight of approximately 500,000or under the name Flexan 130 having a molecular weight of approximately100,000 by the National Starch Company. Such compounds are described inparticular in French Patent 2,198,719.

Alkali metal or alkaline earth metal salts of sulphonic acids derivedfrom lignin and, more particularly, calcium or sodium lignosulphonatessuch as the product sold under the name Marasperse C-21 by the AmericanCan Company and those based on C₁₀ C₁₄ sold by the Avebene Company.

Sulphonic polyacrylamide salts, such as those mentioned in U.S. Pat. No.4,128,631 and more particularly polyacrylamidoethylpropanesulphonic acidsold under the name COSMEDIA POLYMER HSP 1180 by the HENKEL Company.

Polymers containing alkylnaphthalenesulphonic acid salt moieties such asthe sodium salt sold under the name Darvan No. 1 by the Van der BiltCompany.

Polymers containing at least one vinylsulphonic moiety in their chainsuch as, more particularly, the polyvinyl sulphonates having a molecularweight of between 1,000 and 100,000 and particularly their sodium,potassium, calcium or ammonium salts and amine salts such as alkylamineor alkanolamine salts, as well as copolymers containing at leastvinylsulphonic groups with one or more cosmetically acceptablecomonomers such as unsaturated acids chosen from acrylic and methacrylicacids and their esters, amides such as acrylamide or methacrylamide,substituted or unsubstituted, vinyl esters, vinyl ethers andvinylpyrrolidone. These polymers are described more particularly inFrench Patents 2,238,474 and U.S. Pat. Nos. 2,961,431 and 4,138,477.

It is also possible to employ according to the invention amphotericpolymers in place of the anionic polymers or in combination.

The amphoteric polymers consist of A and B moieties distributedstatistically in the polymer chain, where A denotes a moiety derivedfrom a monomer containing at least one basic nitrogen atom and B denotesa moiety derived from an acidic monomer containing one or morecarboxylic or sulphonic groups or alternatively A and B can denotegroups derived from zwitterionic monomers of carboxybetaines; A and Bmay also denote a cationic polymer chain containing secondary, tertiaryor quaternary amine groups in which chain at least one of the aminegroups carries a carboxylic or sulphonic group connected through theintermediacy of a hydrocarbon radical, or else A and B form part of achain of a polymer containing an α,β-ethylenedicarboxylate moiety inwhich one of the carboxylic groups has been caused to react with apolyamine containing one or more primary, secondary or tertiary aminegroups.

These polymers are described in particular in U.S. Pat. Nos. 3,836,537and French Patent 1,400,366, as well as in French Patent Publication79/29,319. It is also possible to employ amphoteric polymers ofdialkylaminoalkyl (meth)acrylate or betainised (methy)acrylamidecontaining the moieties: ##STR3## in which R₁ denotes a hydrogen atom ora methyl group, R₂ denotes an alkylene group containing 1 to 4 carbonatoms, Y denotes O or NH, R₃ and R₄ denote independently of each otherhydrogen, alkyl containing 1 to 4 carbon atoms, the copolymers withacrylic or methacrylic acid esters containing alkyl radicals having 4 to24 carbon atoms and acrylic or methacrylic acid esters containing alkylradicals having 1 to 3 carbon atoms and optionally other monomers suchas N-vinylpyrrolidone, acrylamide, hydroxyethyl or propyl acrylate ormethacrylate, acrylonitrile, styrene, chlorostyrene, vinyltoluene, vinylacetate, and the like, which are known in themselves.

It is also possible to employ in accordance with the invention anioniclatices which are latices whose anionic functional groups are providedeither by polymerisation or copolymerisation of anionic monomers by theusual processes known to those skilled in the art, either by combinationof the anionic free radical originating from the reaction initiator withthe monomer or the monomers in question during the initiation ofpolymerisation of the said monomers or by juxtaposition of these twoprocesses for synthesis or alternatively by introducing end groups by achain transfer reaction in the second process making use of a reactioninitiator.

The process making use of reaction initiators is described in particularin the article by R. M. FITCH "Preparation and characterisation ofcharge stabilized polymer colloids" in "Polyelectrolytes and theirapplications", 51-69 by D. REIDER Publishing Company.

The latices employed more particularly according to the invention resultfrom the polymerisation of various monomers such as styrene, butadiene,acrylonitrile, chloroprene, vinylidene chloride, isoprene, isobutylene,vinyl chloride, and esters of acrylic, methacrylic, vinyl acetic,maleic, crotonic or itaconic acids, employed alone or in a mixture withone or more of the following ion-forming monomers:

acrylic, methacrylic, itaconic, maleic, crotonic, para-styrenesulphonic,vinylsulphonic, 2-methacryloyloxyethylsulphonic and2-acrylamido-2-methylpropylsulphonic acids.

The latices may also be obtained by polymerisation or copolymerisationof the abovementioned ion-forming monomers.

The latices obtained according to the abovementioned second processresult from the use of initiators chosen from redox systems, peroxides,perphosphates, percarbonates, persulphates, peroxidised organic acidssuch as for example peracetic acid, or the persulphate-bisulphate-ironmixture.

The functional monomers employed in the case of chain transfer reactionare chosen from organic thio-acids such as for example mercaptoaceticacid.

Among the anionic latices which may be employed in accordance with theinvention particular mention can be made of the products sold under thefollowing tradenames: KARAMUL 142 ST sold by the FRANCONYX Company whichis an acrylic emulsion; the latices sold under the names PRIMAL B52,PRIMAL K3, PRIMAL TR 485, PRIMAL AS 95 consisting of acrylic aqueousemulsions sold by the ROHM & HAAS Company, containing between 20 and 50%solids; APPRETAN ANT which is a dispersion of an acrylic copolymer, soldby the HOECHST Company; ACRYMUL AM 176 R which is an aqueous emulsion ofan acrylic copolymer containing reactive groups, sold by the PROTEXCompany; NATIONAL 125 4477 and 125 4445 which are aqueous dispersions ofan acrylic copolymer, NATIONAL 125 2833, NATIONAL 125 2869, NATIONAL 1252873 which are emulsions of a vinyl acetate/acrylic acid copolymer soldby the NATIONAL ADHESIVES & RESINS Company; LUCIDENE 347 which is astyrene acrylic acid emulsion, sold by the WILLIAMS Company; SYNTRAN1026 which is an acrylic acid-ethylene-styrene emulsion sold by theINTER POLYMER CORPORATION; COLAPERLE SPA which is an aqueous dispersionof an acrylic copolymer sold by the PCUK Company; a CHEMIGUM LATEX 6271which is a copolymer of carboxylated butadiene and acrylonitrile sold bythe GOODYEAR Company.

It is self-evident that other anionic latices may be employed inaccordance with the invention.

The anionic polymers which are more particularly preferred are thosecontaining a linear uncrosslinked acrylic or methacrylic moiety, amaleic anhydride moiety optionally monoesterified or hydrolysed or agrafted crotonic acid moiety optionally crosslinked or incorporatingmore than one monomer other than vinyl acetate.

The polymers are employed in accordance with the invention eitheraccording to a two-step process including in a first stage theapplication of a composition containing the quaternised protein and in asecond stage the application of a composition containing the anionicpolymer such as defined above, or including in a first stage theapplication of a composition containing the anionic polymer and in asecond stage the application of a composition containing the quaternisedprotein, or by means of a single composition containing, in a solventmedium, the anionic polymer and the quaternised protein.

The compositions employed for applying the polymer or polymers on thekeratinic fibres are compositions containing the said polymers inconcentrations from 0.01 to 10% by weight and preferably inconcentrations of between 0.1 and 5% by weight in a suitable medium fortheir application on these fibres. The pH of these compositions isgenerally between 2 and 11 and preferably between 3 and 10.

It may be adjusted with alkalising or acidifying agents which are knownin themselves.

These compositions may be in various forms such as liquid, cream,emulsion, gel, thickened lotion, or powder; they may contain water aswell as any cosmetically acceptable solvent chosen, in particular, frommonoalcohols, such as alcanols containing 1 to 8 carbon atoms, such asethanol, isopropanol, benzyl alcohol, phenylethyl alcohol, polyalcoholssuch as alkylene glycols, such as ethylene glycol, propylene glycol,glycol ethers such as mono-, di- and triethylene glycol monoalkyl etherssuch as for example ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, diethylene glycol monoethyl ether, employed alone or asa mixture. These solvents are present in concentrations below or equalto 70% by weight relative to the weight of the total composition.

These compositions may also be packaged as aerosol and in that caseapplied in the form of an aerosol spray, or in the form of aerosol foam.

In this form of embodiment it is possible to employ in particular, aspropellant gas, carbon dioxide, nitrogen, nitrogen oxide, volatilehydrocarbons such as butane, isobutane and propane and preferablychlorine-containing and fluorine-containing hydrocarbons.

Preferred compositions may also contain electrolytes such as alkalimetal salts, such as sodium, potassium or lithium salts, these saltsbeing preferably chosen from sulphates, halides, such as chloride,bromide or salts of organic acids such as acetates or lactates, as wellas alkaline-earth metal salts chosen preferably from calcium, magnesiumor strontium carbonates, silicates, nitrates, acetates, gluconates,pantothenates, and lactates.

These compositions may also be in the form of powder or of lyophilysatesto be diluted before use.

The compositions according to the invention may contain any otheringredient usually employed in cosmetics, such as perfumes, colorantswhose function may be to colour the composition itself or the fibres,preserving agents, sequestering agents, thickeners, silicones, softeningagents, foam synergists, foam stabilisers, sunscreens, peptising agents,and anionic, nonionic, cationic or amphoteric surface-active agents ortheir mixtures.

These compositions may be employed in particular in the form of shampoo,rinse lotion, cream or treatment product which can be applied before orafter dyeing or bleaching, before or after shampooing, before or afterpermanent waving or hair straightening and can also have the form of acolouring product and hair setting lotion, blow-drying lotion, orproduct for bleaching, permanent waving or hair straightening.

These compositions are applied preferably on the hair and the nailswhere the best results are found.

A particularly preferred embodiment consists of the use in the form ofshampoo for washing hair.

In this case, these compositions contain anionic, cationic, nonionic oramphoteric surfactants or their mixtures in a concentration of between 3and 50% by weight, preferably between 3 and 20% and their pH is between3 and 10.

A list of the surfactants which may be employed in accordance with theinvention is given in the Applicant Company's French Patent 2,383,660.

Another preferred embodiment consists of the use in the form of rinselotion to be applied mainly before or after shampooing. These lotionsmay be aqueous or aqueous alcoholic solutions, emulsions or thickenedlotions or gels. When the compositions are in the form of emulsions theymay be nonionic or anionic. The nonionic emulsions consist chiefly of amixture of oil and/or fatty alcohol and polyethoxylated alcohol such aspolyethoxylated stearyl or cetylstearyl alcohols and cationicsurfactants may be added to these compositions.

An embodiment which is also preferred and which gives advantageousresults on hair consists of the compositions such as defined above,pressurised in an aerosol device and forming a foam when exposed to air.

The anionic emulsions are formed essentially starting from soap.

When the compositions are in the form of thickened lotion or gel, theycontain thickeners in the presence or absence of solvent. The thickenerswhich may particularly be employed are especially sodium alginates, gumarabic, cellulose derivatives and it is also possible to obtainthickening with a mixture of polyethylene glycol and polyethylene glycolstearate or distearate or with a mixture of phosphoric ester and amide.The concentration of thickener may vary between 0.05 and 15% by weight.

When the compositions are in the form of hair-dressing lotion,hair-shaping lotion or hairsetting lotion, they generally incorporatethe polymers defined above, as well as nonionic polymers if appropriate,in aqueous, alcoholic or aqueous alcoholic solution.

When the compositions of the invention are intended to be employed fordyeing keratinic fibres and in particular human hair, they contain, inaddition to the quaternised protein or proteins and the anionic polymer,at least one precursor of an oxidation dye and/or a direct dye. They mayalso contain any other adjuvant usually employed in this type ofcomposition.

The pH of the dyeing compositions is generally between 7 and 11 and canbe controlled at the desired value by adding an alkalising agent.

The composition according to the invention may also be employed forwaving or straightening hair. In this case, the composition contains, inaddition to the anionic polymer or polymers and the cationic protein,one or more reducing agents, and optionally other adjuvants usuallyemployed in this type of composition. These compositions are intended tobe employed in conjunction with an oxidising composition.

When the polymers are applied according to a two-step process, thecombination of the quaternised protein with the anionic polymer isproduced directly in the region of the fibres.

This process can be employed by applying in a first stage a compositionin the form of pre-lotion containing the quaternised protein and in asecond stage a composition such as for example a shampoo or a dyecontaining the anionic polymers defined above.

According to another alternative form of the invention, a shampoocontaining the quaternised protein can be applied in a first stage and acomposition such as a lotion containing the anionic polymer in a secondstage.

It is also possible to proceed by employing in succession a compositionfor permanent waving, hair straightening, colouring, or bleachingcontaining the quaternised protein and to follow this first treatmentwith a second treatment with a composition containing the anionicpolymer, the latter being put in a composition which may be a shampoo ora simple lotion or alternatively an oxidising solution, particularly inthe case of the permanent waving or colouring compositions.

It is also possible to employ in a first stage a shampoo containing thequaternised protein and in a second stage another shampoo containing theanionic polymer, the pH of the compositions applied in these two stagesbeing capable of being different and adjusted so as to be present at thetime of the application of the composition containing the anionicpolymer under conditions which permit a good deposit of the combinationaccording to the invention on the fibres to be treated.

The following examples are intended to illustrate the invention without,however, being of a limiting nature.

EXAMPLE 1

A shampoo of the following composition is prepared:

    ______________________________________                                        Lexein QX 3000           1.2     g AI                                         Polacrylic acid of approximate                                                                         0.6     g AI                                         molecular weight 3500 sold in 25%                                             strength as AI in water by the                                                ALLIED COLLOIDS Company under the                                             name VERSICOL E5                                                              Sodium alkyl (C.sub.12 -C.sub.14) ether                                                                8       g AI                                         sulphate oxyethylenated with                                                  2.2 moles of ethylene oxide and                                               25% of active ingredient                                                      Water, perfume, preserving agent,                                                                      100     g                                            colorant q.s.                                                                 ______________________________________                                    

The pH is adjusted to 7.5 with sodium hydroxide.

Hair washed with the aid of this shampoo has, once dried, goodsettability as shown by a firmer hairstyle and good shape retention withtime.

EXAMPLE 2

A shampoo with the following composition is prepared:

    ______________________________________                                        Lexein QX 3000             3      g AI                                        Surfactant of formula:     4      g AI                                        R--CHOH--CH.sub.2 --O--(CH.sub.2 --CHOH--CH.sub.2 --O).sub.n H                R: mixture of C.sub.9 -C.sub.12 alkyl radicals                                n: denotes a statistical average value                                        of approximately 3.5                                                          Nonionic surfactant based on poly-                                                                       6      g AI                                        glycerolated (4.2 moles) lauryl                                               alcohol in solution containing                                                approximately 60% active ingredient                                           Polymethacrylic acid of approximate                                                                      0.2    g AI                                        molecular weight 26,000 sold at                                               20% AI in water under the name                                                VERSICOL K13 by the ALLIED COLLOIDS                                           Company                                                                       Sodium chloride            4      g                                           Water, perfume, colorant, preserving                                                                     100    g                                           agent q.s.                                                                    ______________________________________                                    

The pH is adjusted to 6.7 with sodium hydroxide.

Hair washed with the aid of this shampoo has good settability as shownby a firmer hairstyle and good shape retention with time.

EXAMPLE 3

A shampoo of the following composition is prepared:

    ______________________________________                                        Lexein QX 3000            4.5    g AI                                         Triethanolamine alkyl (C.sub.12 -C.sub.14)                                                              10     g AI                                         sulphate containing 40% active ingredient                                     Surfactant of formula:    2      g AI                                          ##STR4##                                                                     with RCO copra fatty acid radical                                             sold under the name MIRANOL C2M conc.                                         by the MIRANOL Company                                                        Copolymer of acrylic acid/methacrylic                                                                   0.15   g AI                                         acid and a monomer consisting of one                                          of their simple esters sold under the                                         name Ultra hold 8 by the                                                      CIBA GEIGY Company                                                            Sodium chloride           4      g                                            Water, perfume, colorant, preserving                                                                    100    g                                            agent q.s.                                                                    ______________________________________                                    

The pH is adjusted to 7.3 with sodium hydroxide.

Hair washed with the air of this shampoo has good settability as shownby a firmer hairstyle and good shape retention with time.

EXAMPLE 4

A shampoo of the following composition is prepared:

    ______________________________________                                        Lexein QX 3000          2.5     g AI                                          Methyl vinyl ether copolymer with                                                                     0.3     g AI                                          maleic anhydride monoesterified with                                          butanol, sold t 50% concentration of                                          active ingredient in ethanol under the                                        name GANTREZ ES 425 by the G.A.F.                                             Company                                                                       Sorbitan monolaurate polyoxyethylenated                                                               5       g AI                                          with 20 moles of ethylene oxide                                               Sodium and magnesium lauryl ether                                                                     7.5     g AI                                          sulphate containing 30% of active                                             ingredient, sold under the name                                               TEXAPON ASV by HENKEL Company                                                 Water, perfume, colorant, preserving                                                                  100     g                                             agent q.s.                                                                    ______________________________________                                    

The pH is adjusted to 7 with sodium hydroxide.

Hair washed with the aid of this shampoo has good settability as shownby a firm hairstyle and good shape retention with time.

EXAMPLE 5

A shampoo of the following composition is prepared:

    ______________________________________                                        Lexein QX 3000             1      g AI                                        7-Trideceth carboxylic acid of formula:                                       CH.sub.3 (CH.sub.2).sub.11 CH.sub.2 --(O CH.sub.2 -CH.sub.2).sub.6            O--CH.sub.2 --COOH         5      g AI                                        containing 90% of active ingredient,                                          sold under the name SANDOPAN DTC acid by                                      the SANDOZ Company                                                            Sodium hemisulphosuccinate of poly-                                                                      14     g AI                                        ethoxylated lauryl alcohol containing                                         40% of active ingredient, sold under                                          the name SETACIN 103 special by the                                           ZSCHIMMER and SCHWARZ Company                                                 Sodium chloride            4      g                                           Polyacrylic acid of approximate molecu-                                                                  0.8    g AI                                        lar weight 27,000 sold at 25% of active                                       ingredient under the name VERSICOL E7 by                                      the ALLIED COLLOIDS Company                                                   Water, perfume, colorant, preserving                                                                     100    g                                           agent q.s.                                                                    ______________________________________                                    

The pH is adjusted to 6.3 with sodium hydroxide.

Hair washed with the aid of this shampoo has good settability as shownby firm hairstyle and good shape retention with time.

EXAMPLE 6

A rinse lotion with the following composition is prepared:

    ______________________________________                                        Lexein QX 3000        0.7       g AI                                          Na polyvinylsulphonate                                                                              0.4       g AI                                          NaCl                  7         g                                             Water, perfume, colorant, preserving                                                                100       g                                             agent q.s.                                                                    ______________________________________                                    

The pH is adjusted to 7.2 with sodium hydroxide.

Hair is washed with the aid of a conventional shampoo: rinsed with theaid of this composition, it has good settability after being dried.

EXAMPLE 7

An after-shampoo is prepared in the form of aerosol foam with thefollowing composition:

    ______________________________________                                        Lexein QX 3000         5       g AI                                           Methyl vinyl ether/maleic anhydride                                                                  0.9     g as AI of                                     copolymer sold under the name GANTREZ                                                                        the acid                                       AN 119 by the G.A.F. Company and                                                                             form                                           employed in the form of sodium salt                                           Sodium chloride        4       g                                              Distearyl dimethylammonium chloride                                                                  0.4     g                                              Water, perfume, colorant, preserving                                                                 100     g                                              agent q.s.                                                                    The pH is adjusted to 7.4 with sodium hydroxide.                              Schedule for filling the aerosol can:                                         Composition 7       90 g%                                                     Propellant Freon 114 (43)/                                                                        10 g%                                                     Freon 12 (57)                                                                                     100 g                                                     ______________________________________                                    

Hair treated with the aid of this composition has good settability asshown by a firmer hairstyle and good shape retention with time.

EXAMPLE 8

An after-shampoo having the following composition is prepared:

    ______________________________________                                        Lexein QX 3000           2       g AI                                         Polyacrylic acid sold at 50% active                                                                    1.6     g AI                                         ingredient under the name GOODRITE K 732                                      by the GOODRICH Company                                                       Mixture of cetylstearyl alcohol and                                                                    5       g AI                                         cetylstearyl alcohol oxyethylenated                                           with 15 moles of ethylene oxide, sold                                         under the name Sinnowax AO by the                                             HENKEL Company                                                                Hydroxyethylcellulose sold under the                                                                   0.5     g AI                                         name CELLOSIZE QP4400H by the UNION                                           CARBIDE Company                                                               Stearyldimethyl benzylammonium chloride                                                                0.8     g AI                                         Sodium chloride          4       g                                            Water, perfume, colorant, preserving                                                                   100     g                                            agent q.s.                                                                    ______________________________________                                    

The pH is adjusted to 5 with sodium hydroxide.

Hair washed with the aid of this shampoo has good settability as shownby a firmer hairstyle and good shape retention with time.

EXAMPLE 9

A shampoo with the following composition is prepared:

    ______________________________________                                        Lexein QX 3000             1.5    g AI                                        Sodium chloride            4      g                                           Partially hydrolysed polyacrylamide of                                                                   0.6    g AI                                        approximate molecular weight 200,000,                                         specific viscosity 3,7 ± 0.5 sold under                                    the name CYNAMER A.370 by the AMERICAN                                        CYANAMID Company                                                              Sodium and magnesium lauryl ether sul-                                                                   10     g AI                                        phate sold at 30% of active ingredient                                        under the name TEXAPON ASV by the                                             HENKEL Company                                                                pH adjusted to 7.8 with sodium                                                hydroxide                                                                     Perfume, preserving agent, q.s.                                               Water q.s.                 100    g                                           ______________________________________                                    

EXAMPLE 10

A shampoo of the following composition is prepared:

    ______________________________________                                        Lexein QX 3000             1.2    g AI                                        Sodium chloride            4.0    g                                           Vinyl acetate/crotonic acid/vinyl neo-                                                                   0.6    g AI                                        decanoate terpolymer sold by the                                              NATIONAL STARCH Company under the name                                        RESINE 28.29.30 neutralised with NaOH                                         Surfactant of formula:     6.0    g AI                                        R--CHOH--CH.sub.2 --O--(CH.sub.2 --CHOH--CH.sub.2 O--).sub.n H                with R: mixture of C.sub.9 -C.sub.12 alkyl                                    radicals                                                                      n: statistical value of 3.5                                                   Triethanolamine alkyl sulphate                                                                           3.0    g                                           pH adjusted to 8.3 with NaOH                                                  Perfume, preserving agent q.s.                                                Water q.s.                 100    g                                           ______________________________________                                    

EXAMPLE 11

An after-shampoo of the following composition is prepared:

    ______________________________________                                        Lexein QX 3000           0.8     g AI                                         Sodium chloride          4.0     g                                            Aqueous dispersion of an acrylic co-                                                                   0.4     g AI                                         polymer sold at 25% of active ingredient                                      under the name NATIONAL 125 2813 by the                                       NATIONAL ADHESIVE & RESINS Company                                            Mixture of cetylstearyl alcohol and                                                                    5.0     g AI                                         cetylstearyl alcohol oxyethylenated with                                      15 moles of ethylene oxide, sold under                                        the name "SINNOWAX AO" by the HENKEL                                          Company                                                                       Stearyldimethylbenzyl ammonium chloride                                                                0.8     g                                            Hydroxyethylcellulose sold under the name                                                              0.5     g                                            "CELLOSIZE QP 4400 H" by the UNION                                            CARBIDE Company                                                               pH adjusted to 5.6 with HCl                                                   Perfume, colorant, preserving agent q.s.                                      Water q.s.               100.0   g                                            ______________________________________                                    

EXAMPLE 12

An after-shampoo with the following composition is prepared:

    ______________________________________                                        Lexein QX 3000             2.0    g AI                                        Vinyl acetate/crotonic acid/vinyl neo-                                                                   0.7    g AI                                        decanoate terpolymer sold by the                                              NATIONAL STARCH Company under the name                                        RESINE 28.29.30, neutralised                                                  Cetyl alcohol              3.0    g                                           Polawax GP 200             1.5    g                                           Distearyldimethylammonium chloride                                                                       0.9    g                                           Sodium chloride            4      g                                           pH adjusted to 7.8 with HCl                                                   Perfume, colorant, preserving agent q.s.                                      Water q.s.                 100    g                                           ______________________________________                                    

EXAMPLE 13

A lotion with the following composition is prepared:

    ______________________________________                                        Terpolymer of vinyl acetate, crotonic                                                                 1       g AI                                          acid and polyethylene glycol, sold by                                         the HOECHST Company under the name                                            ARISTOFLEX A                                                                  Lexein QX 3000          0.25    g AI                                          Ethyl alcohol q.s.      20°                                            pH 8 with 2-amino- 2-methyl-1-propanol                                        Perfume, colorant, preserving agent q.s.                                      Water q.s.              100     g                                             ______________________________________                                    

This composition is applied on washed hair which is shaped and driedwithout having been rinsed after application of the composition.

EXAMPLE 14

A foam with the following composition is prepared:

    ______________________________________                                        Copolymer of methyl vinyl ether with                                                                  1        g AI                                         maleic anhydride monoesterified with                                          butanol, sold at 50% of active ingredient                                     in ethanol under the name GANTREZ ES 425                                      by the GENERAL ANILIN Company                                                 Quaternised protein sold at 30% of                                                                    0.5      g AI                                         active ingredient under the name LEXEIN                                       QX 3000 by the INOLEX Company                                                 pH 7.5 with 2-amino-2-methyl-1-propanol                                       Perfume, colorant, preserving agent q.s.                                      Water q.s.              100      g                                            This composition is packaged in an aerosol device.                            Active principal:   90 g                                                      Propellants: Freons 12/114                                                                        10 g                                                      (50/50 by weight):                                                            Total               100 g                                                     ______________________________________                                    

The foam is applied to clean hair.

After shaping and drying, the hair shows good shape retention.

EXAMPLE 15

The following composition is prepared:

    ______________________________________                                        Lexein QX 3000          0.4      g AI                                         Copolymer of methyl vinyl ether with                                                                  0.8      g AI                                         maleic anhydride monoesterified with                                          butanol, sold at 50% concentration of                                         active ingredient in ethanol under the                                        name GANTREZ ES 425 by the G.A.F.                                             Company and 20% neutralised with 2-amino-                                     2-methyl-1-propanol                                                           pH adjusted to 8 with 2-amino-2-methyl-                                       1-propanol                                                                    Water q.s.              100      g                                            ______________________________________                                    

This composition is applied on nails as a hardener.

We claim:
 1. A composition for the cosmetic treatment of nails and skin,comprising, in a cosmetically acceptable medium which is suitable forapplication to said nails or skin a strongly cationic quaternizedprotein and an anionic latex, or an amphoteric polymer wherein:theanionic functional groups of said anionic latex are produced either bypolymerization or copolymerization of anionic monomers in whichpolymerization or copolymerization is effected either by combination ofan anionic free radical originating from the reaction initiator with themonomer or the monomers during the initiation of polymerisation of saidmonomers or by juxtaposition of these two processes of synthesis or,alternatively, by the introduction of end groups by a chain transferreaction in the second process employing a reaction initiator; saidstrongly cationic quanternized protein has the formula: ##STR5## inwhich A is a protein residue derived from hydrolysates of collagenprotein, R is a lipophilic group containing up to 30 carbon atoms, and Xis an alkylene group containing from 1 to 6 carbon atoms; saidamphoteric polymer contains two moieties, moiety A and moiety B, whichare distributed statistically in said amphoteric polymer chain such thatmoiety A is derived from a monomer that contains at least one basicnitrogen atom and moiety B is derived from an acidic monomer thatcontains at least one carboxylic or sulphonic group, or moieties A and Bare groups that are derived from zwitterionic monomers ofcarboxybetaines or are cationic polymer chains that contain secondary,tertiary or quaternary amine groups such that at least one of said aminegroups includes a carboxylic or sulphonic group connected to said aminegroup via a hydrocarbon radical, or moieties A and B form part of achain of a polymer that contains an α,β-ethylenedicarboxylate moiety inwhich one of the carboxylic groups has reacted with a polyamine thatcontains one or more primary, secondary, or tertiary amine groups; and,the concentration of said strongly cationic quaternized protein and saidanionic latex or amphoteric polymer is between 0.01 and 10% by weight.2. The composition of claim 1, wherein the molecular weight of thequaternized protein is between 1,500 and 10,000.
 3. The composition ofclaim 1, wherein the anionic functional groups of the anionic latex areproduced by polymerization of a monomer selected from the groupconsisting of styrene, butadiene, acrylonitrile, chloroprene, vinylidenechloride, isoprene, isobutylene, vinyl chloride and esters of acrylicmethacrylic, vinyl acetic, maleic, crotonic, or itaconic acid, whereinsaid monomer is polymerized alone or as a mixture with one or more ofthe ion-forming monomers selected from the group consisting of acrylic,methacrylic, itaconic, maleic, crotonic, para-styrenesulphonic,vinylsulphonic, 2-methacryloyloxyethylsulphonic and2-acrylamido-2-methylpropylsulphonic acids.
 4. The composition of claim1, further comprising electrolytes selected from the group consisting ofalkali metal salts and alkaline earth metal salts.
 5. The composition ofclaim 1, wherein the pH is between 2 and
 11. 6. A composition of claim1, that is formulated as a liquid, creams, emulsion, gel, thickenedlotion or powder.
 7. A composition of claim 1, that contains water or amixture of water and a cosmetically acceptable solvent selected from thegroup consisting of monoalcohols containing 1 to 8 carbon atoms,polyalcohols, glycol ethers and mixtures of said monoalcohols,polyalcohols, and glycol ethers.
 8. A composition of claim 1, that isformulated as powder or lyophilizate that is diluted before use.
 9. Thecomposition of claim 1, further comprising perfumes, colorants forcoloring the composition, colorants for coloring the nails or skin,preservatives, sequestering agents, thickeners, silicone, softeningagents, foam synergists, foam stabilizers, sunscreening agents,peptising agents, anionic, nonionic, cationic or amphotericsurface-active agents or mixtures of said surface active agents.
 10. Acomposition of claim 1, which is formulated as a thickened lotion orgel, further comprising thickeners selected from the group consisting ofsodium alginates, gum arabic, cellulose derivatives, mixtures ofpolyethylene glycol and polyethylene glycol stearate or distearate andmixtures of phosphoric ester and amide, wherein the concentration ofthickener is between 0.05 and 15% by weight relative to the total weightof the composition.
 11. The composition of claim 1, wherein theconcentrations of the quaternized proteins and of the anionic latex arebetween 0.01 and 10% by weight.
 12. The composition of claim 11, whereinsaid concentrations are between 0.1 and 5%.
 13. A composition of claim 1that is packaged as an aerosol that is formulated as a spray or foam.14. A composition of claim 13 that is formulated as an aerosol thatforms a foam upon expansion in the air.
 15. A process for hardeningnails, comprising applying a composition of claim 1 on the nails.
 16. Aprocess for the cosmetic treatment of the skin and nails, comprisingapplying a strongly cationic quaternized protein and either an anioniclatex or an amphoteric polymer to the skin or nails,wherein: the anionicfunctional groups of said anionic latex are produced either bypolymerization or copolymerization of anionic monomers in whichpolymerization or copolymerization is effected either by combination ofan anionic free radical originating from the reaction initiator with themonomer or the monomers during the initiation of polymerisation of saidmonomers or by juxtaposition of these two processes of synthesis or,alternatively, by the introduction of end groups by a chain transferreaction in the second process employing a reaction initiator; saidstrongly cationic quaternized protein has the formula: ##STR6## in whichA is a protein residue derived from hydrolysates of collagen protein, Ris a lipophilic group containing up to 30 carbon atoms, and X is analkylene group containing from 1 to 6 carbon atoms; said amphotericpolymer contains two moieties, moiety A and moiety B, which aredistributed statistically in said amphoteric polymer chain such thatmoiety A is derived from a monomer that contains at least one basicnitrogen atom and moiety B is derived from an acidic monomer thatcontains at least one carboxylic or sulphonic group or moieties A and Bare groups that are derived from zwitterionic monomers ofcarboxybetaines or are cationic polymer chains that contain secondary,tertiary or quaternary amine groups such that at least one of said aminegroups includes a carboxylic or sulphonic group connected to said aminegroup via a hydrocarbon radical, or moieties A and B form part of achain of a polymer that contains an α,β-ethylenedicarboxylate moiety inwhich one of the carboxylic groups has reacted with a polyamine thatcontains one or more primary, secondary, or tertiary amine groups; andthe concentration of said strongly cationic quaternized protein and saidanionic latex or amphoteric polymer is between 0.01 and 10% by weight.17. The process of claim 16, wherein said strongly quaternized proteinand either said anionic latex or said amphoteric polymer are applied ina single composition.
 18. The process of claim 16, wherein the anionicfunctional groups of the anionic latex are produced by polymerization ofa monomer selected from the group consisting of styrene, butadiene,acrylonitrile, chloroprene, vinylidene chloride, isoprene, isobutylene,vinyl chloride and esters of acrylic, methacrylic, vinyl acetic, maleic,crotonic, or itaconic acid, wherein said monomer is polymerized alone oras a mixture with one or more of the ion-forming monomers selected fromthe group consisting of acrylic, methacrylic, itaconic, maleic,crotonic, para-styrenesulphonic, vinylsulphonic,2-methacryloyloxyethylsulphonic and 2-acrylamido-2-methylpropylsulphonicacids.